In a bowl, mix together the shrimp, the 1/4 cup olive oil, vinegar, sweet smoked chili rub, and salt. Cover and refrigerate for 1 to 2 hours.
Bring a large pot of salted water to a boil over high heat. Add the pasta, stir well and cook until al dente (tender but firm to the bite), according to package instructions.
Meanwhile, in a large fry pan over medium-high heat, warm 2 Tbsp of olive oil. Drain the shrimp, discarding the marinade, and add the shrimp to the pan. Cook, turning once or twice, until the shrimp are opaque throughout, 1 to 2 minutes. Transfer the shrimp and any pan juices to a plate and cover to keep warm.
Drain the orzo and transfer to a warmed serving bowl. Add the shrimp and their juices to the orzo and stir several times. Add the basil and cheese and gently stir again once or twice.